CN101024205B - Methods for removing metals from plating operation - Google Patents
Methods for removing metals from plating operation Download PDFInfo
- Publication number
- CN101024205B CN101024205B CN2006100647958A CN200610064795A CN101024205B CN 101024205 B CN101024205 B CN 101024205B CN 2006100647958 A CN2006100647958 A CN 2006100647958A CN 200610064795 A CN200610064795 A CN 200610064795A CN 101024205 B CN101024205 B CN 101024205B
- Authority
- CN
- China
- Prior art keywords
- method described
- integer
- metal
- compound
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/206—Manganese or manganese compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Chemically Coating (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Removal Of Specific Substances (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to compounds and methods for removing metals, e.g., ionic cobalt from an electroless plating operation, preferably to levels less than 5 ppm. The metals can then be either landfilled or regenerated for electrowinning and reuse. The invention utilizes an ion exchange media comprised of a silica backbone and functionalized with phosphonate groups.
Description
Technical field
The present invention relates to remove the method for metal, for example from electroless plating membrane operations (electroless platingoperation), remove ionic cobalt, preferably remove the back level less than 5ppm.Then, described metal can be by landfill or for electroextraction with utilize and regenerate.
Background technology
In chemistry and biochemistry industry, use acid catalyst to carry out a large amount of chemical conversion.A large amount of homogeneous phases and heterogeneous catalyst are used, and wherein some need at high temperature come into force and produce quite a large amount of byproducts and refuse.These do not wish that the product and the refuse that obtain must processed and destructions.To method-" Green Chemistry " of more environmental protection-demand given prominence to recycling, more effective and the necessity of catalyst more selectively.This necessity caused to can the catalysis number of chemical research of new material design of conversion.The key request of such raw catelyst is extraordinary heat endurance, height insensitivity to chemical erosion, high functional group load capacity, the structure of fixing and rigidity, best functional group is to avoid resetting and byproduct limited swellability, the insolubility in organic solvent, be easy to purify and high durability high ageing resistance and be easy to the approaching functional group that carries out chemical transformation.In addition, the method for making these catalyst systems must be flexibly so that can produce optimum structure and the shape that is fit to specific reaction.This will be included in macropore and regulate porous between the microcellular structure, be loaded with different functional groups, be easy to generate different metal derivatives and pH scope optionally.
There have been multiple metal and catalyst to be embedded into or to be adsorbed on the surface of silica and other material.One of problem that these systems face is, because active function groups is very faint with being connected usually of silica, and makes the active function groups forfeiture.When new organosilicon stone material requires to have above-mentioned performance, also have firm attachment in the functional group that is connected on multiple metal and the catalyst.Because stricter environmental planning is growing to the demand of removing and reclaim the more effective system of metal from the various solvents that are contaminated with metals and water base refuse and sewage.For example, industry is as the water base effluent of nuclear industry and electroplating industry generation enormous quantity, and this effluent is by undesirable metal ion severe contamination.Used cation-exchanger from solution, to remove metal ion.The kind of employed cation-exchanger mainly is a partial cross-linked polystyrene skeleton organic, that have the sulphonate-base that is connected on the part phenyl ring.The physics of these polystyrolsulfon acid base cation-exchangers and chemical property are subjected to the strong influence of organic essence of condensate skeleton, and therefore the technical field of their application of some disadvantages affect is arranged.These limitations comprise lower temperature tolerance (100-130 ℃), to the sensitiveness of chemical erosion and this can cause breaking fully of polymer matrix, and big swellability, the unavailability in some organic solvent and need swelling so that functional group can be approaching.The organic phospho acid cation-exchanger is also for example being reported in the U.S. Patent No. 5,281,631.These systems are based on the copolymerization product of vinylidene diphosphonic acid and styrene, acrylonitrile and divinylbenzene.Yet, the physics of these organic phospho acid resins and chemical property and closely similar based on the system of polystyrolsulfon acid, so their application also is limited.
Inorganic polymer system such as silica, aluminium oxide and titanium oxide, they do not have these shortcomings, are carried out research as ion-exchanger.Active function groups or metal are connected to these systems by different modes.Yet, these systems face have only low content functional group can with these surface facts that be connected.One of other problem that these systems face is that functional group is removed can in use or leave standstill the time.This is because the connection between the surface atom of functional group and carrier is considerably faint.U.S. Patent No. 4,552,700 and 5,354,831 have described based on sulfonic acid group and have been connected to strongly acidic cation exchanger on the organopolysiloxane skeleton.The material of being reported has general formula (O
3/2Si-R
1-SO
3)
xM
x, R wherein
1Be the alkyl or cycloalkyl segment, M is hydrogen or the monovalence metal ion to tetravalence, and the free valency of oxygen atom is by the silicon atom of other group in the general formula and/or by for example SiO
4/2, R
1SiO
3/2, TiC
4/2, AlO
3/2Deng the cross-bridge member saturated.When these materials during, generally believe with other functional group and compare that the validity of the metal complex of sulfonic acid group and certain limit is limited as cation-exchanger.In addition because sulfonate groups is univalent anion thereby also is restricted, therefore relatively with other functional group, need more these functional groups with metal bonding.
Summary of the invention
The present invention relates to remove the method for metal, for example from the electroless plating membrane operations, remove ionic cobalt, preferably remove the back level less than 5ppm.Then, metal can be by landfill or for electroextraction (reclaim (reclamation)) with utilize and regenerate.The present invention used comprise silica skeleton and by the phosphonic acids alkali with functionalized Ion Exchange Medium.
The specific embodiment
The compound that the present invention uses is as described below:
Formula 1:
Wherein R and R
1Be hydrogen independently respectively, the C of straight or branched
1-40Alkyl, C
2-40Alkenyl or C
2-40Alkynyl, aryl or C
1-40Alkaryl or optional complexation of metal ions M
N+/ n, wherein n is from 1 to 8 integer; The free valency of silicate (silicate) oxygen atom is saturated by following one or more: the silicon atom of other group in the formula 1, hydrogen, the C of straight or branched
1-12Alkyl or cross-bridge member R
3 qM
1(OR
2)
mO
K/2Or Al (OR
2)
3-pO
P/2Or R
3Al (OR
2)
2-rO
R/2M wherein
1Be Si or Ti; R
2Be the C of straight or branched
1-12Alkyl; R
3Be the C of straight or branched
1-6Alkyl; K is from 1 to 4 integer, and q and m are from 0 to 2 integers; M+k+q=4; P is from 1 to 3 integer; R is from 1 to 2 integer; Or other known oxygen metal bridged bond system (oxo metal bridging systems); X, y and z are that integer is so that for segment R
3 qM
1(OR
2)
mO
K/2Or AI (OR
2)
3-pO
P/2Or R
3AI (OR
2)
2-rO
R/2All the time the ratio of the situation x:y+z of Cun Zaiing is from 0.00001 to 100000 variation, and integer z is to 200y from 0 simultaneously.Formula 1 can be abbreviated as XxYyZz, wherein X representative [O
3/2SiCH (CH
2PO (OR) (O R
1)) CH
2CH
2Si O
3/2], Y represents [O
3/2SiCH
2CH
2PO (OR) (O R
1)] and Z representative [O
3/2SiCH
2CH
2CH
2PO (OR) (O R
1)].
About the more details of the used compound of the present invention, their preparation and use are quoted at this as a reference referring to the document of publication number No.U.S.2004/0077889.
The efficient of the above-claimed cpd that the present invention is used can be about 0.5-5mmol/g.Shown in the following Table I, described medium can be reduced to cobalt far below detectable limit.
Table I
| Species of metal ion | Original metal ion concentration (ppm) | Concentration of metal ions (ppm) behind contact w/ medium |
| Cr +3 | 100 | 0 |
| Mn +2 | 100 | 0.05 |
| Fe +3 | 100 | 0.16 |
| Co +2 | 100 | 0 |
| Ni +2 | 100 | 0.12 |
| Pb +2 | 100 | 0.08 |
| Cu +2 | 100 | 0.08 |
| Zn +2 | 100 | 0.07 |
| Cd +2 | 100 | 0.06 |
Preferably about 5-500 μ m of the particle diameter of the above-claimed cpd that the present invention is used are more preferably 20-100 μ m.These materials also can be united use with concentrating metals with nanofilter (nanofilter), then with concentrate by modified silica to remove cobalt.The pH scope of handling is preferably about 6-10, is more preferably about 7.5-9.Described modified silica material can be purchased from Phosphonics Ltd..Method of the present invention is particularly useful on microelectronics industry is used.
The present invention is described by specific implementations, and a lot of other forms clearly of the present invention and change are conspicuous to those skilled in the art.In general appended claim and the present invention should be interpreted as covering all these conspicuous form and changes that drop in the real spirit and scope of the present invention.
Claims (10)
1. method of removing metal from the electroless plating membrane operations comprises adding to described operation comprising with following formula 1 compound compositions:
Wherein R and R
1Be hydrogen independently respectively, straight or branched C
1-40Alkyl, C
2-40Alkenyl or C
2-40Alkynyl, aryl or C
1-40Alkaryl or optional complexation of metal ions M
N+/ n, wherein n is from 1 to 8 integer; One or more are saturated: the silicon atom of other group in the formula 1, hydrogen, straight or branched C by following for the free valency of silicate oxygen atom
1-12Alkyl or cross-bridge member R
3 qM
1(OR
2)
mO
K/2Or Al (OR
2)
3-pO
P/2Or R
3Al (OR
2)
2-rO
R/2M wherein
1Be Si or Ti; R
2Be straight or branched C
1-12Alkyl; R
3Be straight or branched C
1-6Alkyl; K is from 1 to 4 integer, and q and m are from 0 to 2 integers; So that m+k+q=4; P is from 1 to 3 integer; R is from 1 to 2 integer; Perhaps other known oxygen metal bridged bond system; X, y and z are that integer is so that for segment [O
3/2SiCH (CH
2PO (OR) (OR
1)) CH
2CH
2SiO
3/2]
x[O
3/2SiCH
2CH
2PO (OR) (OR
1)]
yAll the time the ratio of the situation x of Cun Zaiing: y+z is from 0.00001 to 100000 variation, and integer z is to 200y from 0 simultaneously.
2. the method described in claim 1, the quantity of wherein said compound is 0.5-5mmol/g.
3. the method described in claim 1 is wherein removed metal to the level less than 5ppm from the electroless plating membrane operations.
4. the method described in claim 1, wherein said metal comprises cobalt.
5. the method described in claim 4, wherein cobalt can be regenerated for recovery.
6. the method described in claim 1, the particle diameter of use therein described compound is 5-500 μ m.
7. the method described in claim 6, the particle diameter of use therein described compound is 20-100 μ m.
8. the method described in claim 1, wherein said compound and nanofilter are united use.
9. the method described in claim 1, wherein the pH of Chu Liing is 6-10.
10. the method described in claim 9, wherein the pH of Chu Liing is 7.5-9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/301,073 US7291273B2 (en) | 2005-12-12 | 2005-12-12 | Methods for removing metals from plating operation |
| US11/301073 | 2005-12-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101024205A CN101024205A (en) | 2007-08-29 |
| CN101024205B true CN101024205B (en) | 2011-07-06 |
Family
ID=38138213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006100647958A Expired - Fee Related CN101024205B (en) | 2005-12-12 | 2006-12-12 | Methods for removing metals from plating operation |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US7291273B2 (en) |
| CN (1) | CN101024205B (en) |
| SG (1) | SG133521A1 (en) |
| TW (1) | TWI393586B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201515411D0 (en) * | 2015-08-29 | 2015-10-14 | Advance Performance Materials Ltd | Substituted materials, process for the production and uses thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3226093A1 (en) | 1982-07-13 | 1984-01-19 | Degussa Ag, 6000 Frankfurt | ORGANOPOLYSILOXANES CONTAINING SULFONATE GROUPS, METHOD FOR THE PRODUCTION AND USE THEREOF |
| US5108615A (en) * | 1989-11-28 | 1992-04-28 | Bio-Recovery Systems, Inc. | Method for recovery of a metal ion from electroless plating solutions |
| US5281631A (en) | 1991-12-20 | 1994-01-25 | Arch Development Corp. | Phosphonic acid based ion exchange resins |
| DE4223539C1 (en) | 1992-07-17 | 1993-11-25 | Degussa | Shaped organopolysiloxanes containing sulfonate groups, process for their preparation and use |
| US5609767A (en) * | 1994-05-11 | 1997-03-11 | Eisenmann; Erhard T. | Method for regeneration of electroless nickel plating solution |
| US6211408B1 (en) * | 1999-03-24 | 2001-04-03 | Celanese International Corporation | Method of removing iodides from non-aqueous organic media utilizing silver or mercury exchanged macroporous organofunctional polysiloxane resins |
| US6514414B1 (en) * | 2000-09-08 | 2003-02-04 | Clariant Finance (Bvi) Limited | Process for separation and removal of iron ions from basic zinc solution |
| GB0100470D0 (en) | 2001-01-09 | 2001-02-21 | Queen Mary & Westfield College | Organopolysiloxanes containing phosphonic groups, methods for the production and use thereof |
| JP4082050B2 (en) * | 2002-03-18 | 2008-04-30 | 東亞合成株式会社 | Method for removing cobalt or cobalt and zinc from aqueous iron chloride solution |
-
2005
- 2005-12-12 US US11/301,073 patent/US7291273B2/en active Active
-
2006
- 2006-12-11 SG SG200608601-1A patent/SG133521A1/en unknown
- 2006-12-11 TW TW095146279A patent/TWI393586B/en not_active IP Right Cessation
- 2006-12-12 CN CN2006100647958A patent/CN101024205B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| TW200735964A (en) | 2007-10-01 |
| TWI393586B (en) | 2013-04-21 |
| CN101024205A (en) | 2007-08-29 |
| US7291273B2 (en) | 2007-11-06 |
| SG133521A1 (en) | 2007-07-30 |
| IE20060900A1 (en) | 2007-07-25 |
| US20070131620A1 (en) | 2007-06-14 |
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Effective date of registration: 20181229 Address after: American Minnesota Patentee after: BL Technology Co., Ltd. Address before: American New York Patentee before: General Electric Company |
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Granted publication date: 20110706 Termination date: 20201212 |